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Structurally Related Scaling Behavior in Ionic Systems.

ABSTRACT: We examine the density scaling properties of two ionic materials, a classic aprotic low molecular weight ionic liquid, 1-butyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide ([BMIm][BETI]), and a polymeric ionic liquid, poly(3-methyl-1,2,3-triazolium bis(trifluoromethylsulfonyl)imide) (TPIL). Density scaling is known to apply rigorously to simple liquids lacking specific intermolecular associations such as hydrogen bonds. Previous work has found that ionic liquids conform to density scaling over limited ranges of temperature and pressure. In this work, we find that the dc-conductivity of [BMIm][BETI] accurately scales for density changes of 17%; however, there is a departure from scaling for TPIL for even more modest variations of temperature and pressure. The entropy of both ionic samples conforms to density scaling only if the scaling exponent is allowed to vary linearly with the magnitude of the entropy.

SUBMITTER: Cheng S

PROVIDER: S-EPMC7497657 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Structurally Related Scaling Behavior in Ionic Systems.

Cheng S S Musiał M M Wojnarowska Z Z Holt A A Roland C M CM Drockenmuller E E Paluch M M

The journal of physical chemistry. B 20200212 7

We examine the density scaling properties of two ionic materials, a classic aprotic low molecular weight ionic liquid, 1-butyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide ([BMIm][BETI]), and a polymeric ionic liquid, poly(3-methyl-1,2,3-triazolium bis(trifluoromethylsulfonyl)imide) (TPIL). Density scaling is known to apply rigorously to simple liquids lacking specific intermolecular associations such as hydrogen bonds. Previous work has found that ionic liquids conform to density scalin ...[more]

PMID: 31999929

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Project description:Charge scaling as an effective solution to the experiment-computation disagreement in molecular modelling of ionic liquids (ILs) could bring the computational results close to the experimental reference for various thermodynamic properties. According to the large-scale benchmark calculations of mass density, solvation, and water-ILs transfer-free energies in our series of papers, the charge-scaling factor of 0.8 serves as a near-optimal option generally applicable to most ILs, although a system-dependent parameter adjustment could be attempted for further improved performance. However, there are situations in which such a charge-scaling treatment would fail. Namely, charge scaling cannot really affect the simulation outcome, or minimally perturbs the results that are still far from the experimental value. In such situations, the vdW radius as an additional adjustable parameter is commonly tuned to minimize the experiment-calculation deviation. In the current work, considering two ILs from the quinuclidinium family, we investigate the impacts of this vdW-scaling treatment on the mass density and the solvation/partition thermodynamics in a fashion similar to our previous charge-scaling works, i.e., scanning the vdW-scaling factor and computing physical properties under these parameter sets. It is observed that the mass density exhibits a linear response to the vdW-scaling factor with slopes close to -1.8 g/mL. By further investigating a set of physiochemically relevant temperatures between 288 K and 348 K, we confirm the robustness of the vdW-scaling treatment in the estimation of bulk properties. The best vdW-scaling parameter for mass density would worsen the computation of solvation/partition thermodynamics, and a marginal decrease in the vdW-scaling factor is considered as an intermediate option balancing the reproductions of bulk properties and solvation thermodynamics. These observations could be understood in a way similar to the charge-scaling situation. i.e., overfitting some properties (e.g., mass density) would degrade the accuracy of the other properties (e.g., solvation free energies). Following this principle, the general guideline for applying this vdW-tuning protocol is by using values between the density-derived choice and the solvation/partition-derived solution. The charge and current vdW scaling treatments cover commonly encountered ILs, completing the protocol for accurate modelling of ILs with fixed-charge force fields.

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Structurally Related Scaling Behavior in Ionic Systems.

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Structurally Related Scaling Behavior in Ionic Systems.

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